Classical epidemiology and xenobiochemical studies have led to a better understanding of the genotoxic effects of environmental contaminants, for example polycyclic aromatic hydrocarbons (PAHs) in humans. Development of assays for carcinogens exposure at the molecular level in humans has therefore been a major focus of research and from the battery of assays that are currently available, both immunological and physico-chemical approaches are being developed. Since each type of assay system clearly has its own advantages and disadvantages, the use of more than one corroborative assay has been of importance. The problems that appear to confront the development of assay systems for human biomonitoring are essentially twofold: the levels of material present in macromolecular complexes challenge the detection limits of conventional assay systems, and complex mixtures of adducted materials confound simple assay systems. A model system using six synthetically modified DNAs was recently proposed to assist in the development of these assays. Two types of immunoassays have been used in these studies: 1) an enzyme- linked immunosorbant assay (ELISA) has been used to detect for PAH-DNA adducts in human DNA and to measure anti-PAH-DNA antibodies in human serum; and 2) ultra-sensitive enzyme-linked radioimmunoassay (USERIA) has been used to determine the presence of PAH-DNA adducts in human lymphocytes. In addition, High Pressured Liquid Chromatography and synchronous fluorescence spectroscopy (SFS) have been used to obtain evidence for the formation of benzo(a)pyrene-diol-epoxide-DNA and benzo(a)pyrene-diol-epoxide-hemoglobin adducts in human peripheral blood.